Recent developments in the chemistry of stable silylenes

Hill, Nicholas J.; West, Robert

doi:10.1016/j.jorganchem.2004.09.012

Cited by 260 publications

(103 citation statements)

References 74 publications

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“…Potential values are referred to the saturated calomel electrode (SCE). Under the experimental conditions employed, the one-electron oxidation of ferrocene occurs 6 H 2 ]SnCl was synthesized as described [52]. Details including its molecular structure will be reported in a forthcoming paper.…”

Section: Methodsmentioning

confidence: 99%

“…This compound is remarkable as it is a dimer in the solid state but undergoes homolytic tin-tin bond dissociation in solution. Both works initiated enormous and still ongoing research activities not only in organotin(II) chemistry but also in the chemistry of their silicon, germanium, and lead congeners, and beyond [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. In course of these studies chemists learned that stabilization of stannylenes can be achieved either kinetically by bulky substituents [4,[20][21][22][23][24] and/or thermodynamically by intramolecular coordination of donor atoms such as nitrogen, phosphorus, and oxygen [25][26][27][28][29][30][31][32][33][34][35][36].…”

Section: Introductionmentioning

confidence: 99%

“…Most remarkably, the 1 H NMR spectrum shows four equally intense resonances for the methyl protons of the i-propyl groups which is indicative for the stereochemical activity of the lone pair at the tin atom.Under UV-light irradiation, the reaction of compound 1 with tungsten hexacarbonyl, W(CO)6 , provided the corresponding transition metal complex [4-t-Bu-2,6-{P(O)(O-iPr) 2 } 2 C 6 H 2 Sn{W(CO) 5 }C 5 H 4 ] 2 Fe (2) as orange crystalline solid in good yield (Eq. (2))…”

mentioning

confidence: 99%

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A ferrocenyl-bridged intramolecularly coordinated bis(diorganostannylene): Synthesis, molecular structure and reactivity of [4-t-Bu-2,6-{P(O)(O-i-Pr)2C6H2Sn}C5H4]2Fe

Henn

Schürmann

Mahieu

et al. 2006

Journal of Organometallic Chemistry

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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A ferrocenyl-bridged intramolecularly coordinated bis(diorganostannylene): Synthesis, molecular structure and reactivity of [4-t-Bu-2,6-{P(O)(O-i-Pr)2C6H2Sn}C5H4]2Fe

Henn

Schürmann

Mahieu

et al. 2006

Journal of Organometallic Chemistry

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“…studies was carried out to determine why these compounds are formed in reactions [4][5][6] . Two major types of Carbenes are Silylene and Germylene.…”

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confidence: 99%

Energetic Property and Aromaticity in various Divalent Carbenes Derivatives: DFT and NMR Studies

Soleymani¹,

Dijvejin²,

Hesar³

2012

Orientjchem.

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“…EPR revealed the formation of new paramagnetic germylene complexes in solutions.The profound interest in the chemistry of low-coordination silicon(II), germanium(II), and tin(II) complexes stems, first of all, from their high reactivity with respect to very different substrates [1][2][3][4][5]. A new line of investigation in this area is the study of low-valence derivatives of Group 14 elements with paramagnetic ligands.…”

mentioning

confidence: 99%

New Paramagnetic Derivatives of N-Heterocyclic Germylenes: An EPR Study

et al. 2005

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The reactions of stable germylenes-1-germa-2,5-diaza-3-cyclopentene derivatives-with 3,6-di-tertbutyl-2-ethoxyphenoxyl and mercury(II) halides in toluene were studied. EPR revealed the formation of new paramagnetic germylene complexes in solutions.The profound interest in the chemistry of low-coordination silicon(II), germanium(II), and tin(II) complexes stems, first of all, from their high reactivity with respect to very different substrates [1][2][3][4][5]. A new line of investigation in this area is the study of low-valence derivatives of Group 14 elements with paramagnetic ligands. The EPR spectra of such complexes can provide rich information on their structures and mechanisms of transformation. The first compounds of this type have been recently reported [6][7][8]. The first crystalline paramagnetic germylene containing the radicalanion acenaphthenediimine ligand was obtained and isolated in [6]. The first paramagnetic stannylenes stable in toluene solutions over a period of several days were obtained by the exchange reaction of tin(II) chloride with some radical-anion lithium diazabutadiene salts [7]. Fixation of some radical species by diamagnetic N-heterocyclic silicon(II) derivatives was reported in [8]. EPR shows that these reactions lead to the formation of unstable silicon(II) derivatives bearing an unpaired electron. Reactions of analogous germylenes with nitroxyl radicals yield only diamagnetic products [9].Here, we report on the first example of generation of paramagnetic three-coordinate germylenes based on diazabutadiene heterocycles in solutions. Radical complexes were obtained by oxidation of substituted 1-germa-2,5-diaza-3-cyclopentenes with mercury halides, as well as by the reaction of the former with the 3,6-di-tert -butyl-2-ethoxyphenoxyl radical.Initial germylenes 1a -1f were obtained as described in [10]. 3,6-Di-tert -butyl-2-ethoxyphenoxyl radical was generated in a solution upon dissociation of the corresponding dimer [11]. EPR spectra were obtained on a Bruker ER 200D-SRC spectrometer (working frequency ~9.5 GHz) with an ER 4111VT variable temperature unit. The g values were determined using diphenylpicrylhydrazyl as the reference ( g = 2.0037). Hyperfine coupling (HFC) constants were obtained by simulation with the WinEPR SimFonia program.All operations for preparation of the complexes were carried out under conditions excluding air oxygen and moisture.It turned out to be impossible to obtain paramagnetic germylenes by the exchange reaction of germanium dichloride with radical-anion lithium diazabutadiene salts as described in [7]. This reaction yields only diamagnetic products. However, the products of the reaction of N , N '-di-tert -butyl-1-germa-2,5-diaza-3-cyclopentene (germylene 1a ) in toluene with mercury(II) chloride or bromide give rise to EPR spectra (Fig. 1). These spectra are well resolved due to small widths (0.08 mT at 290 K) of individual spectral components. The hyperfine structure (HFS) arises from hyperfine coupling of an unpaired electron to magnetic nuclei 1 H (...

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Recent developments in the chemistry of stable silylenes

Cited by 260 publications

References 74 publications

A ferrocenyl-bridged intramolecularly coordinated bis(diorganostannylene): Synthesis, molecular structure and reactivity of [4-t-Bu-2,6-{P(O)(O-i-Pr)2C6H2Sn}C5H4]2Fe

A ferrocenyl-bridged intramolecularly coordinated bis(diorganostannylene): Synthesis, molecular structure and reactivity of [4-t-Bu-2,6-{P(O)(O-i-Pr)2C6H2Sn}C5H4]2Fe

Energetic Property and Aromaticity in various Divalent Carbenes Derivatives: DFT and NMR Studies

New Paramagnetic Derivatives of N-Heterocyclic Germylenes: An EPR Study

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